Hydrogen transfer process



Patented July 14, 1953 UNITED STATE ATENT OFFICE HYDROGEN TRANSFERPROCESS No Drawing. Application February 23, 1950,

Serial No. 145,904

19 Claims. 1

This application is a continuation-in-part of our co-pending applicationSerial Number 788,642 filed November 28, 1947, now abandoned.

This invention relates to a process for effecting hydrogen transferreactions and particu: larly for producing fused ring polycyclichydrocarbons from fused ring bicyclic or polycyclic hydrocarbons inwhich one ring is aromatic while another ring is completelyhydrogenated.

An object of this invention is to produce a polycyclic hydrocarbon withtwo aromatic rings.

Another object of this invention is to condense with itself ahydrocarbon having an aromatic ring fused to a naphthenic ring andhaving a hydrocarbon group containing at least one but not more than twohydrogen atoms combined with the carbon atom bound to the aromatic ring.

A further object of this invention relates to the condensation of5-isopropylindan at hydrogen transfer conditions.

One embodiment of this invention relates to a hydrogen transfer processwhich comprises reacting in the presence of an alkylating catalyst abranched-chain olefin-acting compound and 1 a polycyclic hydrocarbonhaving a saturated ring fused to an aromatic ring and having ahydrocarbon group substituent of at least two carbon atoms having atleast one hydrogen atom combined with the carbon atom bound to a nuclearcarbon atom of said aromatic ring in meta position to said saturatedring and having at least one replaceable nuclear hydrogen atom on saidaromatic ring to form a self-condensation polycyclic hydrocarbon havingat least four rings,

and recovering said self-condensation polycyclic hydrocarbon.

Another embodiment of this invention relates to a process for producinga polycyclic hydrocarbon having at least four rings per molecule whichcomprises reacting in the presence of an alkylating catalyst abranched-chain olefin and a polycyclic hydrocarbon having acycloparaifin ring fused to an aromatic ring and having a hydrocarbongroup substituent of at least two carbon atoms containing a hydrogenatom combined with the carbon atom bound to a nuclear carbon atom ofsaid aromatic ring in meta position to said saturated ring and adjacentto another nuclear carbon atom of said aromatic ring having replaceablehydrogen in ortho positions to said substituent to form aself-condensation hydrocarbon having at least four rings, and recoveringsaid self-condensation hydrocarbon.

Still another embodiment of this invention relates to a process forproducing a polycyclic hydrocarbon having at least four rings permolecule which comprises reacting in the presence of an alkylatingcatalyst a branched-chain olefin and a polycyclic hydrocarbon having acycloparafiin ring fused to an aromatic ring and having a hydrocarbongroup substituent of at least two carbon atoms containing a hydrogenatom combined with the carbon atom bound to a nuclear carbon atom ofsaid aromatic ring in meta position to said cycloparaifin ring andadjacent to another nuclear carbon atom of said aromatic ring having areplaceable hydrogen atom in ortho position to said substituent and tosaid cycloparafiin ring to form a self-condensation hydrocarbon havingat least four rings, and recovering said self-condensation hydrocarbon.

Still another embodiment of this invention relates to a process forproducing a polycyclic hydrocarbon having four rings per molecule whichcomprises reacting in the presence of an alkylating catalyst abranched-chain olefin and a polycyclic hydrocarbon having a,cycloparafiin ring fused to an aromatic ring and having a hydrocarbongroup substituent of at least two carbon atoms containing a hydrogenatom combined with the carbon atom bound to a nuclear carbon atom ofsaid aromatic ring in meta position to said cycloparafiin ring andadjacent to another nuclear carbon atom of said aromatic ring having areplaceable hydrogen atom combined with a nuclear carbon atom of saidaromatic ring to form a self-condensation hydrocarbon having four rings,and recovering said self-condensation hydrocarbon.

A further embodiment of this invention relates to a process forproducing a trialkylcycloalkaaryl(perhydrocycloalka) -indan whichcomprises reacting in the presence of a mineral acid catalyst abranched-chain olefinand a bicyclic hydrocarbon having a saturated ringof at least five and not more than six carbon atoms fused to a benzenering and with a secondary group combined with said benzene ring in metaposition to said saturated ring and with a replaceable nuclear hydrogenatom in ortho position to said alkyl group to form from said bicyclichydrocarbon a self-condensation product comprising essentially atrialkylcycloalkaaryl-(perhydrocycloalka) -indan, and recovering saidtrialkylcycloalkaaryl- (perhydrocycloalka) indan.

A still further embodiment of this invention relates to a process forproducing a trimethyl- 3 cycloalkaaryl- (perhydrocycloalka) -indan whichcomprises reacting in the presence of a hydrofiuoric acid catalyst abranched-chain olefin and a bicyclic hydrocarbon having a saturated ringof at least five and not more than six carbon atoms fused to a benzenering and with an isopropyl group combined with said benzene ring in metaposition to said saturated ring and with a replaceable nuclear hydrogenatom in ortho position to said isopropyl group to form from saidbicyclic hydrocabon a self-condensation product comprising essentially atrimethylcycloalkaaryl-(perhydrocycloalka) indan, and recovering saidtrimethylcycloalkaaryl-(perhydrocycloalka) -indan.

An additional embodiment of this invention relates to a hydrogentransfer process which comprises reacting in the presence of anacid-acting catalyst a branched-chain oleiinic acting compound and apolycyclic fused ring hydrocarbon containing one aromatic ring and analkyl group substituent of at least two carbon atoms and having at leastone hydrogen atom combined with the carbon atom of the alkyl groupattached to the ar matic ring, said alkyl group being attached to thecarbon atom on the aromatic ring which is two carbon atoms removed fromthe point of fusion of the aromatic ring to a saturated ring.

A still additional embodiment of this invention relates to a hydrogentransfer process which comprises reacting in the presence of anacidacting catalyst a branched-chain olefinic acting compound and apolycyclic fused ring hydrocarbon containing one aromatic ring and twosaturated group substituents in which at least one of said substituentshas at least two carbon atoms and at least one hydrogen atom combinedwith the carbon atoms of the saturated groups attached to the aromaticring, said saturated groups being attached to the carbon atoms on thearomatic ring which are one carbon atom removed from the points offusion of the aromatic ring to a saturated ring.

We have developed a method for eirecting a hydrogen transfer between abranched-chain olefinic hydrocarbon and a polycyclic hydrocarbon havinga cycloparamn ring fused to an aromatic ring and also having certainallryl substituents bound to the aromatic ring. Such pclynuclearcompounds have one aromatic ring and an allryl group bound to saidaromatic ring. The alkyl groups must have either one or two hydrogenatoms combined with a carbon atom attached to the aromatic ring; thiscarbon atom is a part of the alkyl group which acts as a hydrogen donorwhereas the olefinic hydrocarbon charged to the process is a hydrogenacceptor.

If the alkyl group which acts as a hydrogen donor is in meta position tothe fused saturated ring, hydrogen transfer will take place providedthat at least one replaceable hydrogen atom is present in the nucleus inortho position to said alkyl donor, that is, this hydrogen transfertakes place in case the alkyl group has one hydrogen atom bound to thecarbon atom of the alkyl group which is attached to the aromaticnucleus. The other alkyl groups that may also be bound to the aromaticnucleus are preferably non-hydrogen donors such as methyl groups.

Thus Compound A which is shown below will not undergo hydrogen transferto give a 5-ring condensation product because no nuclear hydrogen atomsare available on the aromatic ring in ortho position to the isopropylgroup. However,

Compound B will react to form a 5-membered ring condensation productbecause one nuclear hydrogen atom is present in ortho position to theisopropyl group, that is, a nuclear hydrogen atom is combined with thecarbon atom which is adjacent to the nuclear carbon atom to which theisopropyl group is joined, the other two positicns in the benzene ringbeing combined with methyl groups as indicated in Formula B.

i .0 i j 0113 7? H CH3 H CH3 It the alkyl group which acts as a hydrogendonor contains two hydrogen atoms on the carbon atom bound to thearomatic ring, such as a straight-chain alkyl group, then it isnecessary that at least one carbon atom on the aromatic nucleus have areplaceable hydrogen atom, this replaceable hydrogen atom preferablybeing in ortho position to the alkyl group of at least two carbon atoms.

It the alkyl substituent on the aromatic ring is in ortho position tothe saturated or cycloparafiln ring, then a substituent in para positionto the alkyl group which acts as a hydrogen donor is necessary in orderfor a hydrogen transfer reaction to take place.

Thus the isopropyl group in Compound C will not act as a hydrogen donor,it being in ortho position to the saturated ring and in meta position tothe methyl group, whereas Compound D will undergo hydrogen transfer andthe isopropyl group will act as a hydrogen donor, it being in orthoposition to the saturated ring and in para position to the methyl group.Compound D will undergo self-condensation to form a 5-membered ring asindicated hereinafter. In Compound D a nuclear hydrogen atom isavailable in ortho position to the isopropyl group while in Compoundwhich is shown below, no readily replaceable hydrogen atom is present inortho position to the isopropyl group and accordingly a -ringedcondensation compound is not formed.

In Compound F, however, in which a normal prop-yl group is present andone replaceable hydrogen atom is also present on a nuclear carbon atomof the benzene ring, a i-ringed condensation product will be formed,whereas in Compound G where no replaceable hydrogen atoms ar present inthe aromatic ring, no condensation product is produced.

CH3 C HzC HaC- CH: (IJH $112 CH? CH3 C 3 As a result of the hydrogentransfer reaction, the molecules of certain polycyclic hydrocarbonscontaining a substituted aromatic ring undergo a self-condensation toform a hydrocarbon of higher molecular weight. A self-condensation ofthis type is illustrated by the following equations which indicates thecourse of this hydrogen transfer process when applied to a mixture of 5-isopropylindan and 4-methylcyclohexene-1 to produce hydrocarbonscontaining five rings per molecule.

The product (I) of the above indicated reaction may be referred to as:l,3,3-trimethyl-l-(5'- indano) 5,6 dihydro-YH-cyclopent[flindan ac.-cording to A. M. Patterson and L. T. Capell, The Ring Index, ReinholdPublishing Corporation, New York, 1940. Similarly, Compound Ia. isreferred to as 1,3,3-trimethyl-1-(5indano)-6,7-dihydro-SH-cyclopentlglindan.

Similarly, the effect of hydrogen transfer reaction on a mixture of4-methyl-7-isopropylindan and 4-methylcyclohexene-l is indicated in thefollowing equation:

yl)(cycloall'ano) -indan hydrocarbons.

Hydrocarbon l (II) may be. referred. to as 4,6,8,8-tetramethyl 6 (4'-(7'methylindano) 1,2 dihydro-3H-cyclopentie]indan. Compound (II) mayalso be referred to as 1,3,3,6tetramethyl-l- (4'-(7-methylindano)cycllopentano- [e]- indan, although the first-mentioned name ispreferred according to the nomenclature summa rized by A. M. Pattersonand L. T. Capell, The Ring Index.

Similarly, the self-condensation of1,2,3,4-tetrahydro-Gisopropylnaphthalene in the presence of4-methylcyclohexene and liquid hydrogen fluoride occurs as indicated bythe following equation:

+2 CH3 I Ij +2 0 CH3 CH (5H3 Hydrocarbon (III) may be referred to as 1,-

tho) 7-5,6,7 ,8-tetrahydrocyc1ohex [f 1 indan.

The polycyclic hydrocarbons indicated as hydrocarbons (I), (II), and(III) in the above equations are members of a class which may bereferred to as trialkylcycloalkaaryl-(perhydrocycloalka) -indanhydrocarbons. They are all very closely related in structures in thatthey all contain a 1,3,3-tria1lkylindan nucleus together with acycloalkanophenyl group (as an indano, cyclopentanophenyl,cyclopentanomethylphenyl, or cyclohexanophenyl group), combined withthe:

l-carbon atom positionof the 1,3,3-trialkylindan.

nucleus and also with a cyclopentano or cycle-- hexano group fused to thbenzene ring of the:

1,3,3-trialkylindan nucleus.

When the bicyclic hydrocarbon starting material contains on its aromaticring not an isopropyl group substituent in meta position to thesaturated ring but has some other secondary alkyl group substituent insaid meta position and With a replaceable hydrogen atom combined withthe nuclear carbon atom in ortho position to the alkyl group, acting asa hydrogen donor, then the resultant self-condensation product is a1,3,3-trialkyl- 1- (cycloalkanoaryl) -(oycloa1kano) indan in which atleast one of said three alkyl groups is an ethyl group or higher alkylgroup and the remainder of these three alkyl groups may be methyl. Suchcompounds are closely related to thel,3,3-trirnethyl-l-(cycloailkanophen- Thesetrialkylcycloalkanoarylcycloalkanoindan hydrocarbons may also bereferred to as trialkylcycloalkaaryl -(perhydrocycloalka) indanhydrocarbons.

This hydrogen transfer process may be employed also for producing highermolecular weight polycyclic hydrocarbons by interacting a branched-chainolefin and a bicyclic hydrocarbon having a cycloparafiin ring fused toan aromatic ring in which 'one of the nuclear hydrogen atoms in thearomaticringin meta-position to the saturated ring isreplaced by astraightechain' alkyl group such as an ethyl group, a normal propylgroup, a normal butyl group, etc.. Thus the reaction of1,2,3,4-tetrahydroe6-n-propyl naphthalene and 4-methylcyclohexene-1 inthe presence of hydrogen fluoride catalyst may be represented by one orboth of the following equations:

CH3 1 H (IJHa CH1 CH3 I (IJ CH5 CH3 l;

l H3 r CH2 2 (3H3 CH2 l z (Iva) Compounds IV and IVa indicated in theabove equations may be referred to as:

1 (6" (11213",4 tetrahydro 7 n pro D pylnaphtho) -propane.

(Iva) 1 06" (1'., 2, 3', 4 tetrahydronaphtho)) 1 (5 f ('l',2',3',4tetrahydro 7 n-propylnaphtho) propane.

Hydrogen transfer reactions similar to those resulting in the formationof Compounds IV and IVa also occur when a branched-chain olefin, such as4-.methylcyclohexene-l, and 4-methy1-7- normalpropylindan are reacted athydrogen transfer conditions as illustrated in the following equation:

, I (v) t The -resultant Compound V may be referred to -as1-- ('4': 17;@vmethylindanoi) 1- 11- -(5' (4 methyl '7 n propy1indano)) propane.Accordingly, Compounds IV, IVa, and V may be referred to as1,1-di-(cycloalkanophenyl)-alkanes in which one of the cycloalkanophenylgroups has at least one alkyl substituent more than the other.

Thus when the alkyl group of the bicyclic hydrocarbon starting material,as 1,2,3,4-tetrahydro-fi-isopropylnaphthalene or 4-methyl-7-isopropylindan, contains only one hydrogen atom combined with the carbonatom that is attached to the benzene ring, such a bicyclic hydrocarbonundergoes hydrogen transfer with a branchedchain olefin such asmethylcyclohexene to form a higher molecular weight polycyclichydrocarbon containing 5 rings,v whereas if the alkyl group is a normalalkyl group, or another group, as an isobutyl group, also having twohydrogen atoms combined with the, carbon atom attached to the benzenering, then two molecules of the alkyl bicyclic hydrocarbon condense toform a higher molecular weight polycyclic hydrocarbon with two bicyclicgroups joined by a paraffin bridge.

Although the above-indicated equations illustrate the application ofthis hydrogen transfer process to bicyclic hydrocarbons which have abenzene ring fused to a cycloparaifin ring such as a cyclopentane ringor a cyclohexane ring, the process is also applicable to otherpolycyclic aromatic hydrocarbons having a benzene ring fused to asaturated bicyclic or polycyclic ring system. Thus 1,23,49,10 hexahydro6 isopropylanthracene which has the formula may be thought of ascontaining a decalin or decahydronaphthalene structure fused to abenzene ring, the latter also being combined with an isopropyl group.The 1,2,3,4,9,l0-hexahydro-6- isopropylanthracene will thus undergohydrogen transfer with a branched-chain olefmic hydrocarbon or otherolefin-acting compound, t form a higher molecular weight polycyclichydrocarbon having '7 rings per molecule.

Fused bicyclic or polycyclic hydrocarbons which are utilizable asstarting materials in this process contain one aromatic ring while theremaining ring or rings are completely hydrogen ated. Also the aromaticring is substituted by at least one alkyl group which may act as ahydrogen donor in meta position to the fused ring. If two alkyl groupsare combined with the aromatic ring and one of the, alkyl groups is inmeta position to the saturated ring, the other alkyl group, which is amethyl group may occupy any of the other available positions. Ifhowever, two alkyl groups are combined with the aromatic ring and .oneof the alkyl groups acting as a hydrogen donor is attached in orthoposition to the fused ring, the other alkyl group must be attached to anortho position also.

The olefinic hydrocarbons which act as hydrogen acceptors in thisprocess may contain at least one double bond attached to a tertiarycarbon atom or such an olefinic carbon atom may be formed in situ. Theolefinic starting materials suitable for this process have a branchedchain and include such hydrocarbons as trimethylethylene,dihydrolimonene, methylcyclohexene, 1,1,3 trimethylcyclohexene,menthene, other alkylcycloalkenes, etc. The exact type of olefin to beused is dependent on the catalyst and the aromatic hydrocarbon withwhich the hydrogen transfer is to be effected. Thus noctene andcyclohexene, namely, olefins not possessing branched chains, whenreacted with bicyclic aromatic hydrocarbons at operating conditionssimilar to those used with the branchedchain olefins, effect alkylationbut not hydrogen transfer.

In addition to the branched-chain monoolefins mentioned above, otherolefin-acting compounds which are also utilizable in this processcomprise conjugated diolefins containing a tertiary carbon atom,alcohols, ethers, esters of carboxylic acids, tertiary alkylphenols,tertiary cycloalkylphenols, and alkyl halides which may be regarded ascapable of forming branched-chain olefins in situ in the reactionmixture.

The process as herein described is carried out in the presence of anallcylating catalyst at conditions necessary for the hydrogen transferre action. Suitable acid-acting alkylating catalysts include mineralacids, such as sulfuric acid, chlorosulfonic acid, fiuorosulfonic acid,hydrogen fluoride, hydroxy borofluoric acids, fluorophosphoric acids,phosphoric acids, Friedel-Crafts halide catalysts, particularly aluminumchloride, aluminum bromine, ferric chloride, zirconium chloride, andboron fluoride, the latter preferably with hydrogen fluoride. Since insome cases Friedel-Crafts catalysts may cause a migration of alkylgroups within the aromatic ring before the hydrogen transfer reactionoccurs, it is sometimes advantageous to use Friedel-Crafts complexes,such as etherate, alcoholate, etc. for this reaction.

Phosphoric acid catalysts comprise orthophosphoric acid, and alsopolyphosphoric acids such as pyrophosphoric acid, triphosphoric acid,and tetraphosphoric acid. Under certain conditions of operation variousoxide-type catalysts may be used which include activated clays,silica-alumina composites, and other silica-containing materials whichare generally utilizable as catalysts for hydrocarbon cracking.

The operating conditions used in the process are dependent upon thenature of the hydrocarbons being treated and also upon the catalystsemployed. When utilizing strong mineral acids, such as hydrogenfluoride, sulfuric acid, a halosulfonic acid as fiuorosulfonic acid,chlorosul- 'fonic acid, and the like, and also Friedel-Crafts metalhalides as aluminum chloride and aluminum bromide promoted by a hydrogenhalide such as hydrogen chloride, the process is carried out at atemperature of from about -30 to about 100 C. and at a pressure up toabout 100 atmospheres. However, in the presence of hydrogen fluoride,sulfuric acid, and aluminum chloride, and boron fluoride with hydrogenfluo ride catalysts the preferred operating temperature is generallyfrom about to about 50 C. while in contact with ferric chloridecatalysts the preferred operating temeperature is from about 50 to about100 C. Silica-alumina and other synthetic oxide catalysts and clays aregenerally used at a temperature of from about 200 to about 400 C. and ata superatmospheric pressure generally not in excess of about 100atmospheres.

Our process is carried out in either batch or continuous operation. Inbatch operation the usual procedure consists in placing a mineral acidor a Friedel-Crafts catalyst and a portion, generally about 50%, of thearomatic hydrocarbon in a reactor provided with a mechanically drivenstirrer, cooling these materials to a temperature of from about 0 toabout 10 C. and adding thereto with stirring, a solution of the olefinin the remainder of the aromatic hydrocarbon. The reaction mixture isthen separated and the product is washed, dried, and distilled toseparate therefrom the resultant higher molecular weight aromatichydrocarbon. Unconconverted aromatic hydrocarbons recovered in thisdistillation are utilizable in the further operation of the process.

The process is also carried out in a continuous manner by passing thearomatic and branchedchain olefinic or cycloolefinic hydrocarbon througha suitable reactor in which they are contacted in the presence of thecatalyst, the latter either as a liquid or as a solid, depending uponthe catalysts such as sulfuric acid, chlorosulfonic acid, or hydrogenfluoride. The catalytic material is introduced continuously to thereactor which is provided with suitable mixing means and the resultantproduct is then separated into a hydrocarbon layer and a catalyst layer,the latter being returned to further use in the process while thehydrocarbon layer is washed, dried, and distilled as hereinabove setforth. When a solid catalyst such as silica-alumina, clay, or asupported Friedel-Crafts type catalyst is used as a fixed bed in thereactor and the aromatic and cycloolefinic hydrocarbons or otherbranched-chain olefins are passed therethrough, the resultanthydrocarbon product requires no washing and drying treatment and may beseparated by distillation to separate therefrom un-l converted aromaticand cycloolefinic hydrocarbons and to recover the desired polycyclichydrocarbons.

In order to obtain relatively high yields of hydrogen transfer productsincluding higher molecular weight indan hydrocarbons or of arylalkanehydrocarbons by our process, it is necessary to use rather carefullyselected hydrocarbon fractions as charging stocks. As already indicatedherein, only certain types of aromatic hydrocarbons, namely, thosecontaining particular substituents are utilizable as starting mate--rials in this process. Also an olefin which does not have abranched-chain structure such as is present in trimethylethylene,dihydrolimonene, methylcyclohexene, etc. acts as an alkylating agent forthe aromatic hydrocarbon also charged to the process. Accordingly, inorder to obtain hydrogen transfer rather than alkylation, it isnecessary to use a branched-chain olefinic hydrocarbon together with theaforementioned substituted. bicyclic hydrocarbons containing fusedaromatic and cycloparaflinic rings.

The polycyclic hydrocarbon condensation products formed in the processare useful as intermediates in organic synthesis such as in theproduction of dyes, pharmaceuticals, insecticides, plastics, etc. Thusthese polycyclic hydrocarbons may be converted into useful dyes by acombination of nitration, reduction and coupling reactions. Alsochlorination of these polycyclic hydrocarbons produces insecticideseffective against mites, lice, ticks, clothes moths, etc.

The following example is given to illustrate the character of resultsobtained by the use of a specific embodiment of the present invention,although the data presented are not introduced With the intention ofunduly restricting the generally broad scope of the invention.

Anhydrous hydrogen fluoride (97 grams) and '70 grams of.5eisopropyl-2,S-dihydroindene (also generally called 5-isopropylindan)were placed in a copper reactor provided with a mechanically drivenstirrer and cooled externally by an ice bath to C. The reaction mixturewas stirred and to it was added a solution consisting of 43 grams of-methylcyclohexene and 70 grams of -isopropylindan, the latterpreviously prepared by alkylating indan with propylene in the presenceof an acid catalyst. After the addition of the mixture of3-methylcyclohexene and 5-isopropylindan was completed, the resultantreaction mixture was poured into ice, previously cooled to 30 C., thehydrocarbon material was recovered, and then washed, dried, anddistilled. Upon distilling 161 grams of the washed and dried hydrocarbonproduct, the first distillate recovered at atmospheric pressure was 20grams of methylcyclohexane formed in the hydrogen transfer reaction. Theremainder of the reaction product was distilled at a pressure of 4 mm.of mercury and separated into fractions having the following points andrefractive indices.

Fraction 1 corresponded to recovered 5-isopropylindan and Fraction 2corresponded to cycloalkylated indan. Fractions 4 to 6 corresponded to aproduct of the condensation of two molecules of 5-ispropylindan with theliberation of a molecule of hydrogen. Analysis of the hydrocarbonmaterial contained in Fractions 4 to 5 showed 90.50% by weight of carbonand 9.40% by weight of hydrogen, these analytical values correspond ingclosely to 90.57% by weight of carbon and 9.43% by weight of hydrogencalculated for the formula 0241-130. The hydrocarbon condensationproduct present in Fractions 4 to 6 was 1,3,3-trimethyl -1 -(5- indano)-5,6 dihydro -7H- cyclopentEflindan.

We claim as our invention:

1. A hydrogen transfer process which comprises reacting in the presenceof an alkylating catalyst a branched-chain olefin and a polycyclichydrocarbon containing a single aromatic ring and a saturated ring fusedto said aromatic ring and having a hydrocarbon group substituent of atleast two carbon atoms having at least one hydrogen atom combined withthe carbon atom bound to a nuclear carbon atom of said aromatic ring inmeta position to said saturated ring and having at least one nuclearhydrogen atom on said aromatic ring to form a self-condensationpolycyclic hydrocarbon having at least four rings, and recovering saidself-condensation polycyclic hydrocarbon.

2. A process for producing a polycyclic hydrocarbon having at least fourrings per molecule which comprises reacting in the presence of analkylating catalyst a branched-chain olefin and a polycyclic hydrocarboncontaining a single aromatic ring and a cycloparaffin ring fused to saidaromatic ring and having a hydrocarbon group substituent of at least twocarbon atoms containing a hydrogen atom combined with the carbon atombound to a nuclear carbon atom of said aromatic ring in meta position tosaid saturated ring and adjacent to another nuclear carbon atom of saidaromatic ring having hydrogen in ortho positions to said substituent toform a selfcondensation hydrocarbon having at least four rings, andrecovering said self-condensation hydrocarbon;

3. A process for producing a polycyclic hydrocarbon having at least fourrings per molecule which comprises reacting in the presence of analkylating catalyst a branched-chain olefin and a polycyclic hydrocarboncontaining a single aromatic ring and a cycloparaffin ring fused to saidaromatic ring and having a hydrocarbon group substituent of at least twocarbon atoms containing a hydrogen atom combined with the carbon atombound to a nuclear carbon atom of said aromatic ring in meta position tosaid cycloparafiin ring and adjacent to another nuclear carbon atom ofsaid aromatic ring having a hydrogen atom in ortho position to saidsubstituent and to said cycloparaffin ring to form a self-condensationhydrocarbon having at least four rings, and recovering saidself-condensation hydrocarbon.

i. A process for producing a polycyclic hydrocarbon having four ringsper molecule which comprises reacting in the presence of an alkylatingcatalyst a branched-chain olefin and a polycyclic hydrocarbon containinga single aromatic ring and a cycloparafiin ring fused to said aromaticring and having a hydrocarbon group substituent of at least two carbonatoms containing a hydrogen atom combined with the carbon atom bound toa nuclear carbon atom of said aromatic ring in meta position to saidcycloparaffin ring and adjacent to another nuclear carbon atom of saidaromatic ring having a hydrogen atom combined with a nuclear carbon atomof said aromatic ring to form a self-condensation hydrocarbon havingfour rings, and recovering said self-condensation hydrocarbon.

5. A process for producing a polycyclic hydrocarbon having four ringsper molecule which comprises reacting in the presence of an acid-actingalkylating catalyst a branched-chain olefin and a bicyclic hydrocarbonhaving a cycloparafiin ring fused to a benezene ring and having ahydrocarbon group substituent of at least two carbon atoms containingtwo hydrogen atoms combined with the carbon atom bound to a nuclearcarbon atom of said benzene ring in meta position to said cycloparaffinring and adjacent to another nuclear carbon atom of said benzene ringhaving a nuclear hydrogen atom in ortho position to said substituent toform a self-condensation hydrocarbon having four rings, and recoveringsaid self -condensation hydrocarbon.

6. A process for producing a polycyclic hydrocarbon having five ringsper molecule which comprises reacting in the presence of an acid-actingalkylating catalyst a branched-chain olefin and a bicyclic hydrocarbonhaving a cycloparafiin ring fused to a benzene ring and having ahydrocarbon group substituent of at least three carbon atoms containingonly one hydrogen atom combined with the carbon atom bound to a nuclearcarbon atom of said benzene ring in meta position to said cycloparafinring and adjacent to another nuclear carbon atom of said benzene ringhaving a hydrogen atom in ortho position to said substituent to form aself-condensation hydrocarbon having five rings, and recovering saidself-condensation hydrocarbon.

'7. A process for producing a polycyclic hydrocarbon having at leastfour and not more than five rings per molecule which comprises reactingtemperature of from about -30 to about 100 C. a branched-chain olefinand a bicyclic hydrocarbon having a cycloparafiin ring fused to abenzene rings and having a hydrocarbon group substituent of at least twocarbon atoms containing a hydrogen atom combined with the carbon atombound to a nuclear carbon atom of said benzene ring in meta position tosaid cycloparamn' ring and adjacent to another nuclear carbon atom ofsaid benzene ring having a nuclear hydrogen atom in ortho position tosaid cycloparafiin ring to form a self-condensation hydrocarbon havingat least four and not more than five rings, and recovering saidself-condensation hydrocarbon.

8. The process defined in claim '7 further characterized in that saidcatalyst comprises hydrofiuoric acid.

9. The process defined in claim 7 further characterized in that saidcatalyst comprises sulfuric acid.

' 10. A hydrogen transfer process which comprises reacting in thepresence of an acid-acting catalyst a branched-chain ol fin and apolycyclic fused ring hydrocarbon containing one aromatic ring and analkyl group substituent of at least two carbon atoms and having at leastone hydrogen atom combined with the carbon atom of the alkyl groupattached to the aromatic ring, said alkyl group being attached to thecarbon atom on the aromatic ring which is two carbon atoms removed fromthe point of fusion of the aromatic ring to a saturated ring.

11. A process for producing a trialkylcycloalkaaryl-(perhydrocycloalka)-indan which comprises reacting in the presence of a mineral acidcatalyst a branched-chain olefin and a bicyclic hydrocarbon having asaturated ring of at least five and not more than six carbon atoms fusedto a benzene ring and with a secondary alkyl group combined with saidbenzene ring in meta position to said saturated ring and with areplaceable nuclear hydrogen atom in ortho position to said secondaryalkyl group to form from said bicyclic hydrocarbon a self-condensationproduct comprising essentially a trialkylcycloalkaaryl-(perhydrocycloalka)indan, and recovering said trialkylcycloalkaaryl-(perhydrocycloalka) -indan.

12. A, process for producing a trimethylcycloalkaaryl-(perhydrocycloalka) -indan which comprises reacting in the presence of ahydrofluoric acid catalyst a branched-chain olefin and a bicycliehydrocarbon having a saturated ring of at least five and not more thansix carbon atoms fused to a benzene ring and with an isopropyl groupcombined with said benzene ring in meta (5-indano)5,6dihydro-7H-cyclopent[flindan which comprises reacting5-isop-ropy1indan and a branched-chain olefin in the presence of ahydrofluoric acid catalyst at a temperature of from about 30 to about+100 C. toform from said is-opropylindan a self-condensation productcomprising essentially 1,3,3-trimethyl-1-(5indano)-5,6-dihydro-Tl-l-cyclopent lflindan, and recovering said1,3,3-trimethyl-1-(5-in,dano) -5,6-dihydro-7Hcyclopent[f]indan.

14. A process for producing 1,3,3-trimethyl-1- (6' (1,2,3',4'tetrahydronaphtho)) 5,6,7,8 tetrahydrocyclohexEflindan which comprisesreacting l,23,4-tetrahydro-6-isopropylnaphthalene and a branched-chainolefin in the presence of a hydrofluoric acid catalyst at a temperatureof from about -30 to about 100 C. to form from said1,2,3,4-tetrahydro-fi-isopropylnaphthalene a self-condensation productcomprising essentially 1,3,3 trimethyl l (6' (l,2,3',4-,tetrahydronaphtho)) 5,6,7,8 tetrahydrocyclohex- [flindan, andrecovering said 1,3,3-trimethy1-1- (6 (1',2,3,4 tetrahydronaphtho))5,6,'7,8 tetrahydrocyclohex [fl indan. V

15. A 1,2,3 trialkyl 1 (cycloalkanophenyl) cycloalkano) -indan.

16. 1,3,3 trimethyl 1 (5' indano) 5,6- dihydro-VH-cyclop ent [f indan.

17. 4,6,8,8 tetramethyl 6 (4' ('7' methylindano)-1,2-dihydro-3H-cyclopentlelindan.

18. 1,3,3 trimethyl 1 (6 (1,2',3',4- tetrahydronaphtho)) 5,6,7,8tetrahydrocyclohexlflindan.

19. A trialkylcycloalkaaryl (perhydrocycloall a)-indan hydrocarbon.

HERMAN PINES. VLADINIIR N. IPATIEFF.

Thomas Aug. 27, 1946 Mattox May 6, 1947 Number

19. A TRIALKYLCYCLOALKAARYL - (PERHYDROCYCLOALKA)-INDAN HYDROCARBON.